关键词: [Ca24Al28O64]4+:4e-电子化合物/
Ti还原/
第一性原理计算/
电输运特性
English Abstract
Fabrication and electrical transport characteristics of the polycrystalline Ca12Al14O33 electride
Feng Qi1,Zhang Xin1,
Liu Hong-Liang1,
Zhao Ji-Ping1,
Jiang Hao1,
Xiao Yi-Xin1,
Li Fan1,
Zhang Jiu-Xing1,2
1.Key Laboratory of Advanced Functional Materials, Ministry of Education, College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, China;
2.School of Materials Science and Engineering, Hefei University of Technology, Hefei 230009, China
Fund Project:Project supported by the National Natural Science Foundation of China (Grant Nos. 51371010, 51572066, 50801002) and the Natural Science Foundation of Beijing, China(Grant No. 2112007).Received Date:01 September 2017
Accepted Date:05 December 2017
Published Online:20 February 2019
Abstract:The[Ca24Al28O64]4+:4e- (C12A7:e-) electride composed of densely packed, subnanometer-sized cages. This unique structure makes it possess distinctive applications in fields of electronic emission, superconductor, electrochemical reaction. In this paper, we explore a new method to prepare the bulk of C12A7:e- electride. The following areare systematically studied in this work. 1) the condition of preparing bulk of C12A7:e- electride by solid reaction combining spark plasma sintering and reduction with Ti particles at high temperature, CaCO3 and Al2O3 powders are used as raw materials; 2) the first principle calculations of band structure and density of states of the C12A7:e- electride; 3) the analysis of the electrical transport properties of the C12A7:e- electride. The bulk of C12A7:e- electride is successfully prepared by this method, so the results show that the bulk of C12A7:e- electrode with the electron concentration 1018-1020 cm-3 is synthesized at 1100 ℃ and a vacuum pressure of 10-5 Pa for 10-30 h. In the process of Ti reduction, Ti particles become evaporated and deposit on the surface of C12A7, the free O2- atom in the cages diffuse to the sample surface, the Ti vapor reacts with the O2-, forming a loose TiO_x layer. In order to maintain electrical neutrality, the electrons of the free O2- atom leave from the cages, forming the C12A7:e- electride. In addition, the loose TiO_x layer also provides a channel for the diffusion of the O2- atoms in the cage, ensuring the continuation of the reduction reaction. The calculated band structure and density of states of the bulk C12A7:e- electride show that when electrons replace the O2- atoms in the cage, the Fermi level of C12A7:e- crosses over the cage conduction band (CCB). Thus the free movement of the electron is the main reason for the insulator C12A7 to convert into conductor C12A7:e-. At the same time the electrons near the Fermi level in the cages are easy to jump from the CCB to the frame conduction band (FCB). Combination of the above experimental results suggests that the electrons in cages are easier to escape to vacuum under the action of electric field or thermal field, which is the main reason for low work function of C12A7:e-. This way provides an new approach to the realization of the insulator C12A7 converting into C12A7:e- electride. And the C12A7:e- is a good electronic emission material due to low work function, low working temperature, and highly anti-poisoning ability, so this method of preparing bulk C12A7:e- electride provides a good new way to synthesize a new electronic emission material.
Keywords: [Ca24Al28O64]4+:4e-/
Ti reduction/
first principles/
electrical tansport properties
